Triazinyl derivatives as gasoline additives



United States Patent 3,158,450 TRIAZWYL DERIVATTVES AS GASOLINEABDKTIVES Gaetano F. DAlelio, South Bend, Ind, assignor, by direct andmesne assignments, to Dal Mon Research (30., Cleveland, Ohio, acorporation of Delaware No Drawing. Filed Dec. 7, 1961, Ser. No. 157,856'29 Claims. (Cl. 44-63) This invention relates to improvements ingasoline-type motor fuels.

To increase the anti-knock value of gasoline-type motor fuel, such fuelsare modified by the addition of a tetraalkyl lead, such as tetramethyllead or tetraethyl lead with a lesser amount of halohydrocarbon, such asan alkyl or alkylene halide, as for example, ethylene dichloride,ethylene dibromide, carbon tetrachloride, and the like. The mixture of atetraalkyl lead and a haloalkane is known as ethyl fluid and is usedextensively in automotive and aviation gasolines in amounts of 1 cubiccentimeter to 4 or 5 cubic centimeters per gallon of gasoline.

In the modern high compression engine, even though the use of ethylfluid is beneficial, its use tends to cause surface or pro-ignition,which results in rnisfiring and disrupts the regular rhythm of engineoperation. This surface ignition in gasoline containing lead derivativesis due to the deposition of various lead compounds within the combustionchamber of the engine, which thereafter produces hot spots or glowpoints in the combustion chamber, causing pre-ignition andpro-combustion.

Another adverse eifect which results from the use of leaded gasoline ismisfiring of the engine due to sparkplug fouling. Though the use ofhalohydrocarbon scavengers has only partially remedied the problemsresulting from the deposition of lead compounds in the combustionchamber, it has been less effective in the prevention of spark-plugfouling, which particularly in aircraft gasoline combustion engines, isa serious problem.

It has now been found that the above disadvantages accompanying the useof leaded gasoline can be substantially minimized and even eliminated bythe addition of a small amount of certain 1,3,5-triazine phosphonic acidderivatives to leaded gasoline, thereby reducing pre-ignition andspark-plug fouling to a significant degree. The additives of thisinvention are derivatives of 1,3,5-triazines,

represented herein as C N to which is attached, through the carbon atomsof the triazine ring, at least one phosphonium moiety,

Since the triazinyl radical is trivalent, these derivatives can containno more than three such phosphonium groups,

3,158,450 Patented Nov. 24, 1964 The only requirement for the compoundsused in the practice of this invention is that they contain at least onesuch phosphonium group, and thus, though the other valencies of thetriazine ring may be occupied by any monovalent radical, certainadvantages accrue, as hereinafter shown, when more than one phosphoniumgroup is present, or when the other monovalent radicals are especiallyselected to perform a special or selected function. These triazinederivatives may also be expressed by the formula ice in which nrepresents a numerical value of 1 to 3, A represents a radical selectedfrom the class of wherein B is selected from the class of oxygen andsulfur, R represents a radical selected from the class consisting ofhydrogen, a hydrocarbon radical containing from one to twenty carbonatoms, the hydroxy and halogenated derivatives of said hydrocarbonradicals, M represents a metal selected from the class of alkaline andalkaline earth metals, K represents a radical selected from the class ofBR, BM, and NR (where the oxygen derivatives are to be specified K issubstituted for K), and Y represents a monovalent radical. For ordinaryusage the nature of the monovalent radical Y is not critical since theefiect of the phosphonium radical on the lead is not affected. Forexample, Y can be H, R, -BH, Br, -NR, --NRNR halogen, and the hydroxy-,halogeno-, acetoxy, alkoxy, carbamido and sulfamido derivatives of the Rgroup such as However, when it is desirable to impart special propertiesto the triazinyl phosphonium derivatives used in the practice of thisinvention, such as increased solubility in petroleum products, then Rrepresents a hydrocarbon radical possessing from 5 to 20 carbon atoms.When it is desired to impart further special properties to thesecompounds, such as antioxidant properties, and to retain solubility inhydrocarbons, or to have these compounds act as stable halogen carriers,while considering also economic factors and availability of rawmaterials, then, preferably Y is R'-, R'B or R N wherein R representsradicals contining 5 to 20 carbon atoms selected from the class of R,halogenated derivatives of R and hydroxy aryl radicals such as l a a)i:s)2 s is used, whereas if a high carbon content is desired, the higheralcohol esters are satisfactory, thus ll a a) i: P 18 31): 3Furthermore, if a detergent property is desired, the tri azinylphosphonium ester may be saponified to produce the monoor di-salt, thus2 a)[ 19-0 CHE-37 O a a) [ii -0 01211 ONa o lLsONa If a non-ionic typedetergent is desired, the phosphonic acid can be reacted with analkylene oxide to obtain such a product, thus Y a e) wherein n has anumerical value of 3 to 15.

The phosphonium moiety can also act as a carrier of halogen atoms thus t(OCHgCH4Cl)g and 1 (OCH CH C1) It can also be a carrier of anantioxidant structure, thus 0 t -l' '-NHC H4OH OCeH4 It can also servein a joint function as a halogen carrier and antioxidant, such as in themoiety The compounds used in the practice of this invention are preparedreadily by the reaction of a halo-s-triazine with a phosphite ester asfollows:

It is obvious from the foregoing that these additive compounds, becauseof the various reactions that can be effected by the phosphites, P(OR)with either a mono-, di-, or tri-halo triazine, can be synthesized tocontain more than the phosphorus atoms as phosphates or phosphites, andtherefore can perform more functions when used as an additive.Furthermore, since the phosphonium structure is attached to a triaz-inering which contains nitrogen in a relatively inert form, the combustionof these compounds produces oxides of nitrogen which also assist inremoval of combustion cylinder deposits.

The synthesis of typical compounds used in the practice of thisinvention is illustrated in the following examples. Unless specifiedotherwise, parts and percentages recited herein are parts andpercentages by weight.

Example 1 One hundred thirteen (113) parts of cyanuric chloride is addedgradually to 575 parts of triethyl phosphite over a period of 1 hour.During the addition considerable heat is generated and some ethylchloride is liberated. The resultant mixture is maintained at 9046? C.for 1 hour and then allowed to cool to room temperature. The cooled massis extracted with low boiling petroleum ether to remove excess triethylphosphite and then recrystallized from ethyl ether. The crude yield isabout 99 per cent, and the melting point of the recrystallized productis 94-95 C. Analyses show 38.36% carbon and 6.12% hydrogen, whichcorrespond closely with the theoretical values of 36.84% carbon and6.11% hydrogen for the compound having the formula When other phosphitesof the formula P(OR) and P(SR) are used instead of the triethylphosphite with R representing butyl, amyl, cyclohexyl, phenyl,chlorphenyl and acetoxyphenyl, the corresponding triazine phosphoniumand thiophos'phonium derivatives are obtained.

Example II Example I is repeated using an equivalent amount of trimethylphosphite instead of triethyl phosphite and there is obtained.

0' Ca s[( OH3)2]3 of melting point 124.5 C., which on analysis shows C,26.89% and H, 4.68%, which is in good agreement with the calculatedvalues for carbon and hydrogen.

Example Ill Example I is repeated, using molar equivalents oftrin-propyl phosphite instead of triethyl phosphite, and there isobtained.

7 0 caNs -i i afldz as an oil which slowly crystallizes on standing at 0C. Example IV Example I is repeated using molar equivalents of tri-(beta-chloroethyl)phosphite instead of triethyl phosphite and there isobtained melting point 53-54 C., which on analysis shows 25.59% C' and3.38% H, which compares with the theoretical values of 25.86% C and3.45% H respectively.

Example V Example I is repeated using molar equivalents of triallylphosphite instead of triethyl phosphite, and there is obtained which onanalysis and molecular weight determination give values in closeagreement with the theoretical values for this compound. When thetrimethylallyl phosphite is used in equivalent amount instead of thetriallyl phosphite, there is obtained s ai: 2 2)21a Example VI Onehundred fifty (150) parts of are added to 200 parts of carbontetrabromide and 80 parts of bromine added to the mixture at 20-50 C.and there is obtained in solution in ethylene dibromide, the compound.

0 ii a si:P(OCHzCHBrCH Br) 3 This solution can be used in lead gasolineas such, or the halogenated phosphonium triazine derivative isolated byremoval of the carbon tetrabromide under reduced pressure. When themethallyl derivative is used instead of the allyl derivative, there isobtained 1'? CH3 1 caN amoornhnrongBm 3 Example VIZ In a suitablereactor equipped with stirrer and reflux condenser a mixture of 145.5parts of 2,4-diamino-6- is obtained, which on analysis gives values of35.16% carbon, 5.89% hydrogen, 15.35% nitrogen, and 17.21% phosphorus.These values are in close agreement with the theoretical values.

When this diester is allowed to stand at 'room temperature with aniline,the corresponding is obtained.

Example VIII The procedure of Example I is repeated, usingtrioctylphosphite in molar quantities equivalent to triethylphosphite,and there is isolated the compound Similarly, the triesters of decyl,dodecyl, tetradecyl, and octadecyl alcohols are prepared.

Example IX One hundred thirty-seven parts of2-chloro-4,6-dihydroxy-s-triazine prepared from cyanuric chloride by themethod given in J. prakt. Chem, (2), 75, 103 (1907) are reacted with 104parts of trimethyl phosphite according 6 to the procedure of Example I.A quantitative yield of 0 (HO): as)2 is obtained. When an equivalentweight 2,4-dichloro-6- hydroxy-s-triazine is used instead of the2-chloro-4,6-dihydroxy compound, the corresponding derivative HOC N[PO'(OCH is obtained in quantitative yield.

When

is treated with aniline, methyl amine and dietnyi amine respectively,according to the procedure of Example VII, the corresponding amides areobtained respectively,

Example X Two hundred thirty-six parts of HOC H NH(C N )CI preparedaccording to the procedure of US. Patent 2,393- 755, in 250 parts ofbenzene are refluxed ten hours with parts of tri-ni-propyl phosphite.Then the benzene is removed under a reduced pressure, using a Wateraspirator, to give a quantitative yield of crude but relatively pure lHOCaH4NHCa si: 3 02 a When an equivalent amount of (HOC H NH) C N CI(see US. Patent 2,393,755) is used instead of the dichloro-triazine ofthis example, there is obtained 0 i H (HOC HANHM a a- B M Treatment ofthese phosphonic esters with the amines of Example D( by the procedureof Example VII produce the corresponding phosphonamides, whereas whendiethyl amine or decyl amine is used, there is obtained respec tivelyHOCgHaNH-CzNg- Example XI Z-amino-4,6-dichloro-s-triazine preparedaccording to the method of Berichte, 32, 6 91 (1889), is'converted to2-amino-4-hydroxy-6-chloro-s-triazine by the hydrolysis procedure of J.prakt. Chem, .(2), 75, 103 (1907). Thereafter, 136 parts of2-amino-4-hydroxy-6-chloro-striazine are reacted with 250 parts oftri-n-butyl phosphite according to the procedure of Example I, and thereis obtained (HO) z 3 3- edit)? Example XII One hundred thirty-eightparts of 2-amino-4,6-dichloros-triazine are mixed with 250 parts oftri-secondary butyl phosphite and allowed to react in a suitablecontainer at room temperature for twenty-four hours, and at 60 C. for 8hours; there is obtained on recrystallization of the reaction productfrom acetone-water a substantial yield of it (01) (N112) a a (0 41 192Example XIII Two hundred and fifteen parts of2-phenyl-4,6-dichloros-triazine prepared by the procedure of US. Patent1,911, 689 is reacted by the procedure of Example II with 210 parts oftrimethyl phosphite, and there is obtained Treatment of this productwith ammonia, and aniline according to the procedure of Example VIIresults in Example XIV One hundred and nine parts of are heated at 100C. with 210 parts of phenol containing 1 part of magnesium oxide for 14hours or until methanol is no longer released from the reaction. Fromthe reaction product there is obtained When this procedure is repeatedwith p-chloro phenol, there is obtained 0 ll CBHB CINQ[ O 011E401]065114 1 2 Example XV 2,4-di-o-dichlorophenyl-6-chloro-s-triazine isprepared by the method of Chem. Ztg. 36, 378 (1912), and when thisproduct is used in the procedures of Examples VII, IX, and XIV there isobtained respectively Example XVI ll (C4130) (NHQO C GEES) C3N -P (0051111):

Example XVII Thirty parts of 10 parts of 37.1% CH aqueous solution and0.1 part of NaOH are mixed and allowed to stand 48 hours at roomtemperature, or until substantially all of the formaldehyde hasdisappeared and there is obtained a dispersion in Water of the compound.

The addition of 4.5 parts of dimethyl amine or 7 parts of diethyl amineto this compound at room temperature produces, respectively,

O H 1 (CH )nNCHzNHCsNzi:P 2 5): 2

O (Q2H5) 2NG zNH s ai: {I} (O gHsh]: Example XVIII Two hundred ten partsof II (N 2): a a) P M 165 parts of 37% formaldehyde aqueous solution,and 3 parts of KOH are allowed to stand at room temperature withconstant agitation for 48 hours, or until substantially all of theformaldehyde has disappeared and there is obtained a dispersion of thecompound 0 H 11o OH NHhC Ng-(P 0 CH3): which is dried in a vacuum atroom temperature.

Example XIX Two hundred parts of '2,l-di-ethylamirip-dchloro-s-trh azineprepared by the method of JACS 73, 2982 (1951) is reacted with parts oftriethyl phosphite as in the procedure of Example II, and pound r u I BM a a- 2 5):

When 203 parts of P(SC H are substituted for the P(OC H of thisexamplethe corresponding compound,

is obtained, which when reacted with aniline according to the procedureof Example I, yields there is obtained the com- 9 Example XXZ-dimethylaminol,6-dichloro-s-triazine is prepared according to theprocedure of JACS 73, 2982 (1951) and converted to the 4-thiocarbamylmethyl sulfide,

by the method given in US. Patent 2,295,562. This is reacted withtriethyl phosphite by the procedure of Example IX to give ll (CHQNH)(HQNO C CH S) C N -P (O C l-I) 2 Example XXI2-chloro-4,6-dimethoxy-s-triazine is prepared according to the procedureof IACS 73, 2989 (1951) and reacted with one molar equivalent oftriallyl phosphite according to the procedure of Example I yieldsExample XXII 2,4-dichlcro-6-methoxy-s-triazine is prepared according tothe procedure of IACS 73, 2989 (1951) and reacted with two molarequivalents of trimethyl phosphite by the procedure of Example I to giveO (CHaO) 2 2[ i) 02 9212 Substitution of2,4-dichloro-6-phenoxy-s-triazine for the corresponding methoxyderivative in this example produces Example XXIII Sulfanilamide isreacted with cyanuric chloride2,4-dichloro-6-(4-sulfamoylanilino)-s-triazine according to the methodof J. Org. Chem., 24, 643 (1959), and when this compound is reacted withtwo molar equivalents of triethyl phosphite according to the procedureof Example 11, there is obtained the compound When2-chloro-4,6-di-(l-sulfamoylanilino)-s-triazine is used instead of theabove dichloro-compound with at least one molar equivalent of triethylphosphite, there is obtained instead whena-amino-4-chloro-6-(4-sulfamoylanilino)-s-triazine is used instead ofthe dichloro compound, then, there is obtained Example XXIV2-ethyl-4,6-dichloro-s-triazine is prepared according to the method ofUS. Patent 1,911,689 .and converted by reaction with ethyl aminocaproateby the method of US. Patent 2,328,961 to When reacted with one molarequivalent of tribenzyl phosphate by the procedure of Example IIproduces Example XXV Equivalent quantities of2,4-dichloro-6-(Z-hydroxyeth- 19 y1amino)-s-triazine are substituted forthe dichloro-triazine of Example XV and there is obtained a good yieldof HO CHQCHQNHC3N3[JI,IJ (0 0213921 When the2-chloro-4,6-di-(2-hydroxyehylamino)-s-triazine is used with one molarequivalent of the phosphite, there is obtained.

(HO CH2CH2N )2Cs a (0 02135): Example XXVI2,4-dichloro-6-(beta-cyanoethyl sulfide)-s-triazme 15 prepared by themethod of US. Patent 2,295,561 and is treated with two molar equivalentof tri-cyclohexyl phosphite by the procedure of Example II and there isobtained 0 NC CHzCHgSCaNai l (0021 110212 When the above cyanoethylsulfide derivative is replaced by an equivalent molar quantity of6-carbanyl methyl sulfide prepared by the procedure of US. Patent2,295,562, there is obtained 0 z O C 2 -C;\ 3i: (OC5H11)2]2 ExampleXXVI] 2,4-dichloro-6-semicarbazido-s-triazine is prepared by the methodof US. Patent 2,295,565 and treated with two molar equivalent oftridecyl phosphite according to the procedure of Example II and there isobtained 0 NH C ONHNHCaNsi: (0 010E213 2]: Example XXVIII2,4-dichioro-6-ureido-s-triazine is prepared according to the method ofUS. Patent 2,295,563 and reacted with tripropyl phosphite by theprocedure of Example II and there is obtained 0 NH C ONHC;N i (o Caron],Example XXIX 2,4-dich1oro-6-(p-sulfamyl-phenyl carbamyl methyl sulfide)is prepared according to the method of US. 2,316,692 and reacted withtri-(p-bromobenzyl) phosphite by the procedure of Example II and then isobtained 0 H NOgSCAHgNHO C GH;SO N l: (0CH2C6H4B1)g]2 Example XXX2,4-dichloro-6-amino-s-triazine is con tedflo2-parahydroxyphenylcarbamyl methyl sulfide by reaction with HSCH CONHC HOH by the procedure of US. Patent 2,295,562 and when this product isreacted according to the method of Example II, With triethyl phosphite,there is obtained 0 (NH:) (Ho CflENHO C urns) C mi: i (0 0,115), ExampleXXXI Cyanuric chloride is converted to 2,4-dichloro-6-phenyl-s-triazineby the method of U.S. Patent 1,911,689 and by reaction with para-hydroxybenzamide (by the procedure used for HSCR CONH type compound in US.

.1 1 Example XXXII 2,4-di-octadecylamino--monochloro-s-triazine isprepared by the method given in JACS 73, 2982 (1951) and reacted with amolar equivalent of trimethyl phosphite by the procedure of Example II,and the product isolated as which when saponified by refluxing withmethanolic NaOH is converted to (HaIOmNHhCaN -:i. (N3): which iswater-dispersible as wetting agent, emulsifier or detergent.

If the procedure of this example is repeated using 2,4-dichloro-G-octadecylamino s triazine prepared by the method of JACS 73,2982 (1951) and reacted with two molar equivalent of trimethylphosphite, there is obtained 0 t sY uNH) a a)i: P M02 2 which is a moreeffective dispersing agent than the monocompounds. This same behavior isobserved in the lower allcyl derivatives containing a total of at leastcarbon atoms in the aliphatic chain, thus The free acid is readilyliberated from these salts by treatment with excess quantities of stronginorganic acids such as sulfuric or phosphoric acid. The free acids areuseful as rust inhibitors and pickling agents, and have the formula andit (Hn sN )2( a-a)- (011):

respectively.

Other metal salts such as potassium, lithium, calcium, magnesium,silver, copper, titanium, zirconium, molybdenum, etc., such as thoseknown metals which form both inorganic or organic salts can be preparedby the known metathesis reactions or by treatment of reaction of theoxides or hydroxides of such metals with the free s-triazine phopshonicacids.

Example XXXIII Cyanuric chloride is converted to 2,4-dimercapto-6rchloro-s-triazine by the method of l. prakt. Chem. (2), 34, 152 (1886),and when this compound is reacted with molar equivalents of trimethylphosphite according to the procedure of Example 11, there is obtainedEatample XXXIV The procedure of Example I is repeated using molarequivalents of diphenylmethyl phosphite instead of triethyl phosphiteand there is obtained o H a e)i: t t)2 ,a The utility of the s-triazinylphosphonium compounds used in the practice of this invention may beillustrated gasoline in the following tests and has the followingdistillation characteristic.

(Cctane rating, 98.5.)

to which is added 4 cc. of tetraethyl lead per gallon of fuel, to whichmay be added ethylene dibromide (EDB) as a scavenger. The amount of EDBadded used is expressed in the term, Theory EDB, which designates theamount of scavenger required to react stoichiometrically will all of thelead anti-detonant so that all of the lead atoms react with all of thehalogen atoms to form PbXg, and thus one theory of halogen scavengercontains two halogen atoms for each atom of lead in the lead anti-.-detonant;

The term Theory S-T-P designates the amount of striazinyl phosphoniumcompound required to react stoichiometr-ically with all of the lead sothat all of the lead atoms and all of the phosphorus atoms to form whichmay be expressed also as Pb(PO and thus only two phosphorus atoms arerequired for each three atoms of lead. Thus it may be seen that one moleof aNa) R): a will be 4.5 Theory S-T-P, while 0 (GaNa)[ R)2]2 will be 3Theory S-T-P, and

, also have EDB theory value, thus using gasolines of wide boiling rangeand with various octane ratings. A typical gasoline used as a referenceO C3N3[%(OCH2CH2G1)2]3 will be 3 Theory EDB and 4.5 Theory S-T-P.

0 omiimoomonnromnml will be 6 Theory EDB and 4.5 Theory S.T.P.

A suitable engine (such as defined in ASTM-D-908-55 and in ASTMD-357-33)suitably instrumented with electrical pressure indicators and electricalionization gap Table I.

TABLE 1 Percent STP Additive Theories Theories Increase S-'lP EDB inmisfiring time None 1 0 (d CaNaIP (0 04119213 0. 1 0. 250 O. 2 0. 5 3250. 2 0. 1 365 0. 3 0. 6 385 ll CaNaIP (0 CuHsh]: 0. 2 0. 8 400 H C3N3[P(0 CoH4C1)2]a V O. 2 0. 6 450 l] C3N3[P(OCH2OH201)2]3 0.6 O 400 0.6 0 1450 ll (CaNs)[P (OCH CHBICHzBIMa 1.0 0 405 0. 5 0 435 0. 7 0. 05 440(1.? C1C H5O(C3N3)[P (O CaH4C1)z]z 0.3 0,2 415 0. 05 1. O 285 (C5H1NH)zCsN3P-O C2115 0. 2 O. 8 385 (H) (CsNa)[P (0 CsH7)2]3 0. 5 0. 5 345Example XXXVI The engine suitably instrumented as in the previousexample to detect abnormal ignitions and pressure rises in thecombustion chamber is operated with the reference gasoline containing2.7 cubic centimeters of tetramethyl lead in the following cycles,simulating driving conditions equivalent to 1 hour at 60 miles per hour3 hours at 30 miles per hour 6 hours of start and stop drivingconsisting of 2 hours idling, 2 hours accelerating to 30 miles per hour,and 2 hours decelerating to idling for a total of ten hours for thecycle, which is repeated 10 times for a total of 100 hours.

The compositions of Example XXXIV are compared in this engine under thecycle given, and all of the compositions containing S-T-P when comparedwith the composition containing no S-TP and 1 Theory EDB show a verysubstantial decrease in the percentage of pre-ignition which result inmisfirings.

It also may be seen from Table I that the S-T-P compounds can be usedalone or in conjunction with halohydrocarbon scavengers.

When the preceding tests are repeated using the correspondingthiophosphonium compounds, improved results are likewise noted.

The invention claimed is: p

1. A fuel consisting essentially of gasoline, a minor amount of atetraalkyl lead anti-detonant suflicient to impart anti-knock propertiesto said fuel and 0.0005-3 moles, per mole of said tetraalkyl leadanti-detonant, of a s-triazinyl phosphonium compound having at least oneand no more than three phosphonium radicals attached to the carbon atomsof said s-triazinyl nucleus, said phosphonium radical being selectedfrom the class consisting of radicals, wherein B is an atom selectedfrom the class consisting of oxygen and sulfur, R represents a radicalselected from the class consisting of hydrogen, hydrocarbon radicalshaving no more than 20 carbon atoms therein, and derivatives of saidhydrocarbon radicals having only derivative groups attached theretoselected from the class consisting of hydroxy and halo radicals, Krepresents a radical selected from the class consisting of -BR, BM andNR and M is a metal selected from the class consisting of alkali andalkaline earth metals.

2. A fuel consisting essentially of gasoline, a minor amount of atetraalkyl lead anti-detonant suflicient to impart anti-knock propertiesto said fuel and 0.0005-3 moles, per mole of said tetraalkyl leadanti-detonant, of a s-triazinyl phosphonium compound having at least oneand no more than three phosphonium radicals attached to the carbon atomsof said s-triazinyl nucleus, said phosphonium radical having the formulawherein R represents a radical selected from the class consisting ofhydrogen, hydrocarbon radicals having no more than 20 carbon atomstherein, and derivatives of said hydrocarbon radicals having onlyderivative groups attached thereto selected from the class consisting ofhydroxy and halo radicals, K represents a radical selected from theclass consisting of OR, OM, NR M is a metal selected from the classconsisting of alkali and alkaline earth metals.

3. A fuel of claim 2 wherein said anti-detonant is selected from, theclass of tetra-ethyl and tetra-methyl lead.

4. A fuel of claim 1 wherein said anti-detonant is selected from theclass of tetra-methyl and tetra-ethyl lead.

5. A fuel consisting essentially of gasoline, a minor amount of atetraalkyl lead anti-detonant suflicient to impart antiknock propertiesto said fuel and 0.0005-3 moles, per mole of said tetraalkyl leadanti-detonant, of a s-triazinyl phosphonium compound having at least oneand no more than three phosphonium radicals attached to the carbon atomsof said s-triazinyl nucleus, said phosphonium radical having the formula7. The fuel of claim lin which said phosphonium compound is s a s s) 2]a 8. The fuel of claim 1 in which said phosphonium compound is C N [PO(OCH CH Cl) 3 15 9. A fuel of claim 8 in Which said anti-detonant isselected from the class of tetra-methyl and tetra-ethyl lead.

10. A fuel of claim 1 in which said phosphonium 11. A fuel of claim 10in which said anti-detonant is selected from the class of tetra-methyland tetra-ethyl lead.

12. A fuel of claim 1 in which said phosphonium compound is C3N3 CHZBI')2] 3 13. A fuel of claim 12 in which said anti-detonant is selected fromthe class of tetra-methyl and tetra-ethyl lead.

14. The fuel of claim 1 in which said phosphonium compound is 15. A fuelof claim 14 in which said anti-detonant is selected from the class oftetra-methyl and tetra-ethyl lead.

compound is 25 16. The fuel of claim 1 in which said phosphonium G 5 )2K 2 5)Q 17. The fuel of claim 1 in which said phosphonium compound isNH2 C3N3[PO(OC5H11)2]2 18. The fuel of claim 1 in which said phosphoniumcompound is s a s 17)2]a 19. The fuel of claim 1 in which saidphosphoniu'm 2,685,581 Coover Aug. 3, 1954 2,751,384 Coover et al June19, 1956 3,011,998 DAlelio Dec. 5, 1961 FOREIGN PATENTS 565,182 CanadaOct. 28, 1958 572,281 Canada May 5, 1959

1. A FUEL CONSISTING ESSENTIALLY OF GASOLINE, A MINOR AMOUNT OF ATETRAALKYL LEAD ANTI-DETONANT SUFFUCIENT TO IMPART ANTI-KNOCK PROPERTIESTO SAID FUEL AND 0.0005-3 MOLES, PER MOLE OF SAID TETRAALKYL LEADANTI-DETONANT, OF A S-TRIAZINYL PHOSPHONIUM COMPOUND HAVING AT LEAST ONEAND NO MORE THAN THREE PHOSPHONIUM RADICALS ATTACHED TO THE CARBON ATOMSOF SAID S-TRIAZINYL NUCLEUS, SAID PHOSPHONIUM RADICAL BEING SELECTEDFROM THE CLASS CONSISTING OF